Abstract

A fully quantum mechanical dynamical calculation on the photodissociation of molecular chlorine is presented. The magnitudes and phases of all the relevant photofragment T-matrices have been calculated, making this study the computational equivalent of a “complete experiment,” where all the possible parameters defining an experiment have been determined. The results are used to simulate cross-sections and angular momentumpolarization information which may be compared with experimental data. The calculations rigorously confirm the currently accepted mechanism for the UV photodissociation of Cl2, in which the majority of the products exit on the C 1Π1u state, with non-adiabatic couplings to the A 3Π1u and several other Ω = 1 states, and a small contribution from the B state present at longer wavelengths.